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711.
Ekeltchik I Gun J Lev O Shelkov R Melman A 《Dalton transactions (Cambridge, England : 2003)》2006,(10):1285-1293
A new versatile family of chelating agents based on bis(hydroxyamino)-1,3,5-triazines, BHTs, is described. The properties of different BHT ligands are determined by electrochemistry, spectroscopy and titrimetry revealing high redox stability, transparency in the visible range, and diprotic acid-like behaviour in the 5-9 pH range. The iron(III) and iron(II)-BHT complexes were studied revealing high affinity of BHTs to iron(III). Electrochemical studies show exceptional preference of the BHT ligands to iron(III) over iron(II), this, in addition to their small size and their fast and reversible electrochemistry makes them potentially useful electrochemical redox couples for the low end of the aqueous potential window (<0.6 V, vs. NHE). The synthetic versatility of the new ligands allows easy tuning of the hydrophobicity, redox potential, and to some extent the stability constant of the complexes by alteration of the peripheral groups appended to the BHTs. 相似文献
712.
Ravirajan P Peiró AM Nazeeruddin MK Graetzel M Bradley DD Durrant JR Nelson J 《The journal of physical chemistry. B》2006,110(15):7635-7639
We report on the effect of nanoparticle morphology and interfacial modification on the performance of hybrid polymer/zinc oxide photovoltaic devices. We compare structures consisting of poly-3-hexylthiophene (P3HT) polymer in contact with three different types of ZnO layer: a flat ZnO backing layer alone; vertically aligned ZnO nanorods on a ZnO backing layer; and ZnO nanoparticles on a ZnO backing layer. We use scanning electron microscopy, steady state and transient absorption spectroscopies, and photovoltaic device measurements to study the morphology, charge separation, recombination behavior and device performance of the three types of structures. We find that charge recombination in the structures containing vertically aligned ZnO nanorods is remarkably slow, with a half-life of several milliseconds, over 2 orders of magnitude slower than that for randomly oriented ZnO nanoparticles. A photovoltaic device based on the nanorod structure that has been treated with an amphiphilic dye before deposition of the P3HT polymer yields a power conversion efficiency over four times greater than that for a similar device based on the nanoparticle structure. The best ZnO nanorod:P3HT device yields a short circuit current density of 2 mAcm(-2) under AM1.5 illumination (100 mW cm(-2)) and a peak external quantum efficiency over 14%, resulting in a power conversion efficiency of 0.20%. 相似文献
713.
Stopped-flow kinetic studies of a HSX-Mn-SalophOMe (1) catalyst provide spectroscopic evidence for the direct generation of a manganese(V) oxo salophen from a manganese(III) perbenzoate. The O-O bond heterolysis reaction that produces the oxo is not facilitated by intramolecular proton transfer from the acid hanging group of the HSX platform. Instead, the hanging group stabilizes the catalyst against oxidative degradation and, consistent with recent predictions of theory, is geometrically matched to promote the end-on coordination of a H2O2 substrate prior to its oxidation at the manganese(V) oxo center. 相似文献
714.
Hedin-Dahlström J Rosengren-Holmberg JP Legrand S Wikman S Nicholls IA 《The Journal of organic chemistry》2006,71(13):4845-4853
[structures: see text] A class II aldolase-mimicking synthetic polymer was prepared by the molecular imprinting of a complex of cobalt (II) ion and either (1S,3S,4S)-3-benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (4a) or (1R,3R,4R)-3-benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (4b) in a 4-vinylpyridine-styrene-divinylbenzene copolymer. Evidence for the formation of interactions between the functional monomer and the template was obtained from NMR and VIS titration studies. The polymers imprinted with the template demonstrated enantioselective recognition of the corresponding template structure, and induced a 55-fold enhancement of the rate of reaction of camphor (1) with benzaldehyde (2), relative to the solution reactions, and were also compared to reactions with a series of reference polymers. Substrate chirality was observed to influence reaction rate, and the reaction could be competitively inhibited by dibenzoylmethane (6). Collectively, the results presented provide the first example of the use of enantioselective molecularly imprinted polymers for the catalysis of carbon-carbon bond formation. 相似文献
715.
α-Zr phosphate (hereafter referred to as ZrP) based composites were prepared by melt blending in order to improve the flame retardancy properties of polyamide 6 (PA6), polyethylene terephthalate (PET), polypropylene (PP) and ethylene vinyl acetate copolymer (EVA). Different morphologies are distinguishable by electron microscopy: PA6-ZrP seems to be a nanocomposite by Transmission Electron Microscopy (TEM) whereas PET-, PP- and EVA-ZrP blends appear micro-composites by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. ZrP acts as flame retardant in PA6 reducing the total heat evolved and consequently the heat release rate during the combustion measured by cone calorimetry. Moreover, ZrP reduces the flammability of PET and EVA acting in synergistic effect with phosphorous based flame retardants. Indeed, it is showed that it is possible to reduce the amount of phosphorous flame retardant adding ZrP to reach UL94 classification V0 for both polymers. 相似文献
716.
We demonstrate how to tailor the spatial distribution of gold nanoparticles (Au-NPs) of different sizes within polystyrene (PS) thin, supported, film hosts, thereby enabling the connection between the spatial distribution of Au-NPs within the polymer film and the optical properties to be determined. The real, n, and imaginary parts, k, of the complex refractive indices N = n(λ)+ik(λ) of the nanocomposite films were measured as a function of wavelength, λ, using multivariable angle spectroscopic ellipsometry. The surface plasmon response of films containing nearly homogeneous Au-NP distributions were well described by predictions based on classical Mie theory and the Drude model. The optical spectra of samples containing inhomogeneous nanoparticle distributions manifest features associated with differences in the size and interparticle spacings as well as the proximity and organization of nanoparticles at the substrate and free surface. 相似文献
717.
Cara L. Nygren M. E. T. Bragg John F. C. Turner 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(1):m4-m6
In the title compound, [ZrCl2(C14H12N)2(C4H8O)2]·1.5C6H6, the Zr atom is pseudo‐octahedral, with two Cl atoms in trans positions and two tetrahydrofuran molecules in cis positions. The two 3,6‐dimethylcarbazolyl ligands are in cis positions and are canted with respect to one another. The two Zr—N distances are 2.1148 (18) and 2.1236 (18) Å, and the N—Zr—N angle is 95.08 (7)°. The title compound crystallizes as the benzene solvate, with one of the benzene molecules positioned on an inversion center. 相似文献
718.
Nicole Lahanas Pavel Kucheryavy Roger A. Lalancette Jenny V. Lockard 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(3):304-312
Studying the axial ligation behavior of metalloporphyrins with nitrogenous bases helps to better understand not only the biological function of heme‐based protein systems, but also the catalytic properties of porphyrin‐based reaction sites in other biomimetic synthetic support environments. Unlike iron porphyrin complexes, little is known about the axial ligation behavior of Mn porphyrins, particularly in the solid state with Mn in the +3 oxidation state. Here, we present the syntheses and crystal and molecular structures of three new high‐spin manganese(III) porphyrin complexes with the different amine‐based axial ligands imidazole (im), piperidine (pip), and 1,4‐diazabicyclo[2.2.2]octane (DABCO), namely bis(imidazole)(5,10,15,20‐tetraphenylporphyrinato)manganese(III) chloride chloroform disolvate, [Mn(C44H28N4)(C3H4N2)2]Cl·2CHCl3 or [Mn(TPP)(im)2]Cl·2CHCl3 (TPP = 5,10,15,20‐tetraphenylporphyrin), (I), bis(piperidine)(5,10,15,20‐tetraphenylporphyrinato)manganese(III) chloride, [Mn(C44H28N4)(C5H11N)2]Cl or [Mn(TPP)(pip)2]Cl, (II), and chlorido(1,4‐diazabicyclo[2.2.2]octane)(5,10,15,20‐tetraphenylporphyrin)manganese(III)–1,4‐diazabicyclo[2.2.2]octane–toluene–water (4/4/4/1), [Mn(C44H28N4)Cl(C6H12N2)]·C6H12N2·C7H8·0.25H2O or [Mn(TPP)Cl(DABCO)]·(DABCO)·(toluene)·0.25H2O, (IV). A fourth complex, chlorido(pyridine)(5,10,15,20‐tetraphenylporphryinato)manganese(III) pyridine disolvate, [Mn(C44H28N4)Cl(C5H5N)]·2C5H5N or [Mn(TPP)Cl(py)]·2(py), (III), acquired using different crystallization methods from published data, is also reported and compared to the previous structures. 相似文献
719.
Hole transport in two fluorene-arylenediamine copolymers is studied by means of time-of-flight (ToF) and space-charge-limited dark-injection (SCL DI) transient current methods. Non-dispersive and dispersive hole transport is observed for a range of sample thicknesses, applied electric fields and temperatures. 相似文献
720.